“梳形”含氟功能聚合物的构建与应用

含氟化合物因具耐热性、耐化学性和低表面能等优异性能,在设计具有特殊功能和特定化学物理性质的功能聚合物时展现出优秀的特性。然而目前大部分含氟聚合物仍是通过传统的自由基聚合获得,难以对聚合物的聚合过程进行调控,导致具有新型结构的含氟聚合物的构建较为困难。随着可控/活性自由基聚合方法的发展,如原子转移自由基聚合(atom transfer radical polymerization, ATRP),可逆加成-断裂链转移聚合(rever-sible addition-fragmentation chain transfer polymerization, RAFT)和开环易位聚合(ring opening metathesis poly-merization, ROMP)等,构建新型结构的含氟聚合物成为可能。通过对含氟聚合物的聚合过程和结构的精准控制,结合“grafting-from”、“grafting-to”和“grafting-through”三种接枝方法可得到“梳形”结构的含氟聚合物。由于含氟链段的高温自迁移性,将含氟链段作为“梳段”,使其具有独特的物理化学性质,在光电、生物医药等高端...     

聚4-乙烯基吡啶原位修饰PVDF膜及其负载磷钨杂多酸催化剂的研究

以聚偏氟乙烯(polyvinylidene fluoride,PVDF)微滤膜为基膜,4-乙烯基吡啶(4-vinylpyridine,4VP)为功能单体,采用表面引发电子活化再生原子转移自由基聚合(SI-AGET ATRP)法在基膜表面原位改性,并通过接枝聚合物侧链上的吡啶基团与Keggin型磷钨杂多酸(H3PW12O40·n H2O,HPW)之间的静电作用,制备了新型混合催化膜.实验结果表明,接枝聚合过程表现出"活性"/可控表面引发接枝聚合性质,基膜表面接枝聚合物量随聚合反应时间呈现线性增加,当反应时间为16 h,聚合物接枝量达到2.25 mg/cm2,聚合物接枝量的增多致使其相互堆积并坍塌,造成膜表面出现块状聚集体.然后,利用溴代十六烷对接枝聚合物进行季铵化改性,制得表面含有吡啶鎓盐的阳离子复合膜,通过接枝聚合物侧基中的吡啶和吡啶鎓盐基团与磷钨杂多酸之间的静电作用促使其在改性膜表面上有效负载.负载后的磷钨杂多酸均匀的分布在膜表面及孔道中,并保持其化学结构.负载催化剂前后膜的接触角从80.4°减小到57.8°,体现了亲水性催化剂的负载对膜表面润湿性的显著影响.     

表面引发的原子转移自由基聚合法在聚偏二氟乙烯表面制备可控的聚甲基丙烯酸甲酯刷

采用表面引发的原子转移自由基聚合法(ATRP)在聚偏二氟乙烯(PVDF)表面制备结构可控的聚甲基丙烯酸甲酯刷。通过碱处理和紫外光照溴代的方法,将ATRP引入到PVDF表面; 然后采用ATRP法将甲基丙烯酸甲酯接枝到溴代的PVDF表面。采用傅里叶变换红外光谱和X-射线光电子能谱对改性前后PVDF表面的结构进行了表征。结果表明甲基丙烯酸甲酯成功地接枝到了PVDF表面。     

氟烯烃的活性/可控自由基聚合研究进展

含氟聚合物具有优异而独特的性能,主要是通过氟烯烃的聚合反应合成的。自从上世纪90年代以来,活性/可控自由基聚合反应获得极大的进展,发展了多种活性自由基聚合的方法,为聚合物的精确设计、合成提供了强有力的手段。氟烯烃的活性/可控自由基聚合反应研究始于上世纪70年代,碘转移聚合已经成功地应用于含氟热塑性弹性体的商业化生产。文献已经报道的氟烯烃活性/可控自由基聚合反应包括碘转移聚合(ITP)、烷基硼自由基聚合、原子转移自由基聚合(ATRP)和可逆加成断裂链转移聚合(RAFT)或黄原酸酯交换法(MADIX)等。通过这些方法可以制备出分子量确定、结构多样化的含氟聚合物,如嵌段、接枝和遥爪聚合物等,使含氟聚合物的应用范围得到进一步拓展。本文结合本课题组的研究工作,对氟烯烃活性/可控自由基聚合反应的研究进展进行了简要综述。     

PVDF基两性离子交换树脂的辐射合成及性能

以聚偏氟乙烯(PVDF)树脂为基材,采用共辐射接枝方法,在PVDF树脂上接枝苯乙烯(St)/甲基丙烯酸二甲氨基乙酯(DMAEMA)二元单体,随后对接枝产物进行磺化和质子化反应引入磺酸基和叔氨基正离子得到了一种新型的PVDF基两性离子交换树脂.红外光谱、X射线光电子能谱(XPS)、热重和扫描电镜(SEM)分析证明了辐射引发接枝共聚及功能化反应的成功进行.接枝反应条件如溶剂、剂量和二元单体浓度对接枝率(GY)有明显的影响.随着接枝率的增加,功能树脂的离子交换容量随之增大,但接枝链St与DMAEMA的摩尔比不变,其阳离子及阴离子交换容量最大分别可达2.16 mmol/g,1.06 mmol/g.     

(甲基)丙烯酸氟烷基酯的“活性”/可控聚合

带氟烷基侧链的(甲基)丙烯酸氟烷基酯聚合物是一类具有独特表面性能和光学特性的氟聚合物,传统的自由基共聚合由于无法调节聚合物的微细结构和氟原子的分布,限制了该类聚合物在更广领域的应用.活性聚合为聚合物分子设计和合成提供了一个有效方法,利用活性聚合方法可以获得预期结构和性能的含氟嵌段聚合物材料.由于引入了氟烷基侧链,(甲基)丙烯酸氟烷基酯的活性聚合又有其特殊性,本文针对它的活性阴离子聚合、基因转移聚合、活性自由基聚合等方面作一综述.     

表面光接枝原理,方法及应用前景

介绍了表面光接枝的原理,方法和应用前景,表面光接枝主要是用芳酮引发有机材料产生表面自由基,从而引发单体聚合生成表面接枝链。实施方法有气相法,液相法和连续液相法。表面光接枝应用领域广泛,可用于聚合材料的表面改性以及表面功能化。     

主链或侧链含二茂铁的聚合物的合成和应用

由于二茂铁基聚合物独特的结构和性能,其在电化学、生物医学及光学等领域具有广阔应用前景。开发新型二茂铁基聚合物并探索其应用已经成为科研工作者的研究热点。本文主要综述主链或侧链含二茂铁的聚合物的合成及应用。其中合成主链含二茂铁的聚合物的方法主要有缩聚法和开环聚合法等。合成侧链含二茂铁的聚合物的方法主要有自由基聚合法、原子转移自由基聚合法和可逆加成断裂链转移聚合法等。最后,对二茂铁基聚合物的应用前景进行了展望。     

表面接枝聚甲基丙烯酸二甲氨乙酯的pH响应型纤维素纸基材料

使用电子转移再生引发剂原子转移自由基聚合(ARGET ATRP)在滤纸表面接枝聚甲基丙烯酸二甲胺乙酯(PDMAEMA),成功制备了具有p H响应性能的新型纤维素纸基材料.分别在苯甲醚和甲醇中进行该接枝聚合反应,发现在甲醇中接枝效率更高.通过游离引发剂生成的均聚物研究了滤纸表面聚合物侧链的分子量及分子量分布.均聚物的GPC曲线表明聚合物分子量随反应时间增加而增加,分子量分布为1.4~1.6.通过FTIR、SEM及接枝率的测量对改性滤纸进行表征,结果表明PDMAEMA在滤纸表面的接枝聚合具有可控性,通过控制反应时间可控制聚合物在滤纸表面的接枝量.在不同p H条件下对改性滤纸进行静态水接触角的测量,发现其疏水性随p H升高而增大,体现出该纸基材料的p H响应特性.     

氟碳端基聚合物合成及其表面吸附性能

综述了近十年来氟端基聚合物的合成,表征及其在表面吸附行为的研究成果。通过含有氟烷基的引发剂或终止剂在活性阴离子聚合反应或自由基聚合反应中使聚合物接上氟端基。已经成功地利用活性阴离子聚合反应合成了氟端基聚苯乙烯,通过含氟自由基引发烯类单体（如丙烯酸,乙烯硅等）可在相应聚合物链上引入氟端基,另外,聚合物的化学改性方法也可将氟基团接在聚合物链端（如氟基聚氧乙烯,氟端基聚合物具有的表面活性,当水溶液中或聚     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.